Sulfurized unsaturated ketones



Patented Aug. 22, 1950 S TAT E S 'PA'TE-N '1 OYFF-TI 'SULFUKIZEDWSATURATED v.KE'IL01\IES No'Drawing. ApplicationMarchi29, 1945, 'Serial No.':585,572

5 Glaims. 1

This invention has to do with new vchemical compounds or reaction products which may be generally des'ignated'ras sulfurized "unsaturated lket'ones oras sulfur-containing:reac'tionproducts of unsaturated ketones and elementary sulfur.

The present invention is predicated upon the :discovery that the mom-pounds or srea'ction prod- :ucts .econtemplated herein when hlended lvcith i-a viscous mineral .oil fraction such 'as hydrocarbon lubricating oil, :will improve various "properties of the oil. )Fonexample, these compounds or me- =action products :will inhibit oxidation :of the :oil, themeb retarding the :formation 50f sludge .and acidic products. They also retard changes-in viscosity, in athe 5.011, with temperature rohange [during use. In addition, some of the compounds .or reaction products are -'characterized :by :the ability to depresszthe pounpointof :oils.

It :is too be understood,?however, that .the present invention is mot :concernedwwith mineral oil -compositions, such compositions ,rforming the subject matter of :our :copending application Serial No.

of which the present application is a continuation-in-part and to 1-which.ref-erence:is made .ior ,iunther details in ;the-cemposition ofthese compounds orreaction products.

:It is also te -be understood that .the use .of the compounds or reaction products contemplated herein is not confined to the improvement :of mineral oils. .Eor example, they may be used as cutting ioils, rubber accelerators, extreme pressure lubricantsand as intermediates in the production of other chemical compositions. .iNumerous other uses and applications of'these com- -pounds or reaction products will be readily aptype described may be jrepl'esentedby' the general wherein is hydrogen or anali-phatic group containing at "least one carbon atom, and preferably containing fir-om :one to ten carbon atoms; R is a methylene :group, n is a whole number from zero to tem; and R. is :an (aliphatic zgroup :containing at least one carbon atom, and .Wh'ennon- =tain'ing twoor "more :carbon atoms may he .satura'ted or unsaturated. Typical iketones 10f zthis type are phorone, .allyl :zacetone, zdiallyl racetone. -dioleyl ketone, et1c.

It will be apparent :rrom rg'eneral formula =(.-I) EUhat t'he unsaturated iceton'es may :be rsymmetr ical or-unsymmetrical remixed) iketones, and that the symmetrical ketones, which aretpreterred herein, will be represented :by the .fiollowjing general formulasitll) n 'o=o-m'.,,- o- 1r,.- o=r| R wherein it, :R' and .12 areas defined above. It will .be seen, f-therefore, "that the symmetrical ketones are characterized by the linkage wherein R andm are-aspteViouSly defined above. Particularly preferred of the ketones having this structure is .dioleyl ketone.

it is believed that the chemical reaction involved in the suliur-ization of the aforesaid ketones may be represented by the following Equation III.

wherein R, R and .n .are as previously defined. This representation is supported by the fact that practically no hydrogen sulfide is evolved during the reaction.

While completely sulfurized ketones of the type shown in Equation III are preferred herein, those 'sulfurized ketones in which not all of the olefin groups are 'sulfurized are effective impro-ving :7 agents and, accordingly,are contemplated'iierein.

"-In *general th'e siilfurized ktones of this invention are prepared by reacting :a lre'tone of the type described :above with elementary sulfur at elevated temperatures until all ot the sulfur has chemically combined. It is considered that ol the sulfur has chemically combined with the ketone when the sulfurized ke'tone obtained therewith is non-corrosive, as -indioated by only a slight tarnish -of discoloration of :a polished copper strip, -'-i-mmersed in a l-%-*=blend :of the reaction product in mineral oil and heated to 150 C. for 3 hours. Although the amount of elementary sulfur used in the preparation may be varied considerably, such as from about to about 40%, it is preferred to use from about 5% to about by weight of the ,ketone used. While elevated temperatures greater than about 150 C. may be used, the preferred temperature range is from about 175 C. to about 195 C. The preferred temperature range has been found to be particularly advantageous inasmuch as undesirable side reactions, which produce unsatisfactory by-products, are kept to a minimum. Consequently, less refining of the non-corrosive sulfurized ketone is necessary. During the reaction, it is desirable, but not necessary, to introduce a non-oxidizing or inert gas such as nitrogen into the reaction mixture; the use of an inert gas at this stage makes it possible to obtain a lightercolored product and minimizes the formation of undesirable by-products. Sulfurizcd ketones so obtained may be further refined, to improve their color by contact with activatedclay or other decolorizing materials.

It has been found that the color of the ketone used in the reaction with sulfur greatly influences the color intensity of the sulfurized product obtained therefrom. For example, when a light, pale-yellow oleone (dioleyl ketone) is heated with sulfur for 4 hours, the brown non-corrosive viscous liquid which results imparts only a slight discoloration to a mineral -oil when blended therewith in minor proportions. However, when a less refined, green oleone is sulfurized and blended as before, a considerably darker mineral oil composition is obtained. The procedure outlined above may be modified by the use of an inert diluent such as a petroleum oil during the sulfurization of the ketone. The diluent will then be removed after the reaction has proceeded to EXAMPLE 1 (a) Reaction mixture 200 grams of oleone (dioleyl or diheptadecenyl ketone) 24 grams elementary sulfur Nitrogen gas (b) Procedure Twenty-four (24) grams of sulfur Were added slowly over a /3 hour period to 200 grams of oleone in a reaction vessel equipped with a mechanical stirrer, upright condenser, thermometer and an inlet tube extending to within a few inches above the reaction mixture. The nitrogen gas is introduced through the inlet tube in order to maintain a non-oxidizing atmosphere. During the addition of sulfur the reaction mixture is stirred and heated from about 110 C. to about 150 C. The reaction is mildly exothermic, and the temperature was raised slowly up to about 175 C. where it was held for 4 hours. The reaction was considered complete, that is, that all of the sulfur was chemically combined, when the reaction product caused only a small amount of tarnish or discoloration on a (11) Reaction mixture 100 grams of phorone 23.2 grams of elementary sulfur Benzene Nitrogen gas (b) Procedure Sulphur and phorone were mixed together in a-reaction vessel equipped as described in Example 1 (b). The mixture was heated to 150-160 for 2 hours, during which time the mixture was stirred and nitrogen gas was bubbled therethrough in order to maintain a non-oxidizing medium. Twenty grams of Super- Filtrol (a decolorizing clay of the activated montmorillonite type represented by the ideal formula Al2Si4O1o(OH)z-nmO (wherein n. is an integer), which has been activated by a suitable acid treatment) Was then added to the reaction mixture, and the resulting mixture was stirred for about 15 minutes at C. The mixture was then filtered (through Super-Filtrol), and the filter aid (Super-Filtrol) was washed with benzene, the benzene washings being combined with the filtrate. The benzene was then removed from the filtrate by distilling the latter to a maximum temperature of C. at 5 mms. pressure. The benzene-free product thus obtained was then distilled and three fractions obtained. The first fraction, 30 grams, was obtained at l10-l70 C. at 5 mms. pressure; it was a yellow-red oil containing 6.8% sulfur. The second fraction, 21 grams, was obtained at -190 C. at 5 mms. pressure; it, too, was a yellow-red oil, but contained 17.3% sulfur. The third fraction, 13 grams, was the residue; it was tar-like in char acter and contained a higher percentage of sulfur than either fraction one or two.

It is to be understood that although we have described certain preferred procedures for preparing the reaction products contemplated hereand H H H Rt-tR'..cR.. ot R ll s s in which formulae, R represents a radical selected from hydrogen and an alkyl group having from one to ten carbon atoms, R represents a methylene group, n represents a whole number from zero to ten and R." represents an aliphatic radical having from one to ten'carbon atoms and which may contain an olefinic bond, the total number of carbon atoms in said sulfurized aliphatic ketone being from about 5 to about 35' 5. As a new composition of matter, the compound FERDINAND P. OTTO. RONALD E. MEYER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,179,066 Smith Nov. 7, 1939 2,254,756 Segessemann Sept. 2, 1941 2,372,160 Morris Mar. 20, 1945 2,372,161 Morris Mar. 20, 1945 2,419,586 Otto et a1. Apr. 29, 1947 

1. AS A NEW COMPOSITION OF MATTER, A SULFURIZED ALIPHATIC KETONE SELECTED FROM THE SULFURIZED ALIPHATIC KETONES REPRESENTED BY THE GENERAL FORMULAE: 